JP5972694B2 - Fe (II) -substituted MEL type zeolite, gas adsorbent containing the same, method for producing the same, and method for removing nitric oxide and hydrocarbon - Google Patents

Fe (II) -substituted MEL type zeolite, gas adsorbent containing the same, method for producing the same, and method for removing nitric oxide and hydrocarbon Download PDF

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JP5972694B2
JP5972694B2 JP2012159149A JP2012159149A JP5972694B2 JP 5972694 B2 JP5972694 B2 JP 5972694B2 JP 2012159149 A JP2012159149 A JP 2012159149A JP 2012159149 A JP2012159149 A JP 2012159149A JP 5972694 B2 JP5972694 B2 JP 5972694B2
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JP2014019602A (en
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賢 小倉
賢 小倉
慶治 板橋
慶治 板橋
達也 大久保
達也 大久保
パラニ エランゴバン シャンムガム
パラニ エランゴバン シャンムガム
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ユニゼオ株式会社
国立大学法人 東京大学
国立大学法人 東京大学
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    • C01B39/36Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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    • B01D2257/702Hydrocarbons

Description

  The present invention relates to an Fe (II) -substituted MEL zeolite, a gas adsorbent containing the same, and a method for producing the same. The present invention also relates to an adsorbent for adsorbing and removing nitrogen monoxide gas and hydrocarbon gas in a gas phase such as exhaust gas of an internal combustion engine, and a method for removing nitrogen monoxide gas and hydrocarbon gas from the gas phase.

It has been proposed to use zeolite ion-exchanged with iron ions as a catalyst for exhaust gas purification of automobiles (see Patent Documents 1 to 3). For example, Patent Document 1 discloses a support obtained by ion-exchange of a beta zeolite having a SiO 2 / Al 2 O 3 molar ratio of 15 to 300 with 0.1 to 15% by mass of Fe 3+ ions, Denitration catalysts having ferric oxide supported on a support are described.

Patent Document 2 has a skeletal structure in which the Si content attributed to Q 4 of the zeolite skeleton observed in a 29 Si MAS NMR spectrum is 35 to 47% by mass, and has a molar ratio of SiO 2 / Al 2 O 3 . It is described that a beta-type zeolite having a ratio of 20 or more and less than 100 is ion-exchanged to carry Fe 3+ and is brought into contact with exhaust gas containing nitrogen oxides.

Patent Document 3 describes a method for producing a NO x adsorbent. In this method, an impregnation step of impregnating ZSM-5, mordenite, or beta zeolite with an aqueous iron chloride solution to form an iron chloride-containing zeolite, and the iron chloride-containing zeolite at 330 ° C. to 500 ° C. in an atmosphere not containing moisture. An ion exchange step of ion exchange of Fe by heating at ° C., and a heat treatment step of heat-treating the iron chloride-containing zeolite after the ion exchange step in a non-oxidizing atmosphere.

International Publication No. 2006/011575 Pamphlet JP 2007-076990 A JP 2008-264702 A

  However, when performing catalytic removal of nitric oxide, if oxygen is present in the exhaust gas at a high concentration or if the temperature of the exhaust gas is low, nitrogen monoxide is effective even if the above-described materials are used. It is not easy to remove by adsorption.

  The subject of this invention is providing the MEL type | mold zeolite which can eliminate the various fault which the prior art mentioned above has.

As a result of intensive studies, the present inventors have used the above-mentioned object by using an Fe (II) -substituted MEL zeolite that is ion-exchanged with divalent iron and has a specific SiO 2 / Al 2 O 3 ratio. Has been found to be achieved.

That is, the present invention provides an Fe (II) -substituted MEL zeolite having an SiO 2 / Al 2 O 3 ratio of 10 or more and 30 or less and ion-exchanged with Fe (II) ions.

  The present invention also provides a gas adsorbent containing the Fe (II) -substituted MEL zeolite.

Furthermore, the present invention provides a MEL zeolite having a SiO 2 / Al 2 O 3 ratio of 10 or more and 30 or less dispersed in a water-soluble aqueous solution of divalent iron and mixed and stirred. The present invention provides a method for producing an Fe (II) -substituted MEL zeolite having a step of supporting Fe (II) ions.

Furthermore, the present invention relates to an Fe (II) -substituted MEL type zeolite having a SiO 2 / Al 2 O 3 ratio of 10 or more and 30 or less and ion-exchanged with Fe (II) ions, and a gas containing nitrogen monoxide or nitric oxide. And a method for removing nitric oxide, wherein the nitric oxide is adsorbed on the Fe (II) -substituted MEL-type zeolite.

Further, in the present invention, the SiO 2 / Al 2 O 3 ratio is 10 or more and 30 or less, and the Fe (II) -substituted MEL zeolite ion-exchanged with Fe (II) ions is brought into contact with hydrocarbon or a gas containing hydrocarbon. Thus, there is provided a method for removing hydrocarbons by adsorbing the hydrocarbons to the Fe (II) -substituted MEL zeolite.

  According to the present invention, an Fe (II) -substituted MEL zeolite useful for catalytic removal of various gases and a method for producing the same are provided. In particular, according to the present invention, when catalytic removal of nitrogen monoxide and hydrocarbons is performed, even if the amount of Fe (II) introduced into the MEL zeolite by substitution is small, nitrogen monoxide and hydro Carbon can be adsorbed and removed.

FIG. 1 is a process diagram for producing a pre-substitution MEL zeolite used in the present invention.

Hereinafter, the present invention will be described based on preferred embodiments thereof. The present invention relates to an Fe (II) -substituted MEL zeolite obtained by ion exchange of MEL zeolite with Fe (II) ions. The present invention also relates to a gas adsorbent containing the Fe (II) -substituted MEL type zeolite. Fe (II) ions, [AlO 2] in MEL-type zeolite - that is a cation ion exchange existing on the site, is supported on the MEL type zeolite. The important point in the present invention is that the iron ion ion-exchanged with the cation contained in the MEL-type zeolite is Fe (II) ion. When the iron ion ion-exchanged with the cation is Fe (III) ion, a desired level of gas removal effect cannot be exhibited. The inventor believes that this reason may be related to the use of MEL-type zeolite having a specific physical property value described later.

  When the iron ion to be ion-exchanged with the cation is Fe (III) ion, the desired level of gas removal effect cannot be expressed. This is because the Fe (II) -substituted MEL type used in the present invention is used. This does not prevent the zeolite from supporting Fe (III) ions. That is, the Fe (II) -substituted MEL zeolite is allowed to carry Fe (III) ions.

  In the present invention, examples of the gas to be adsorbed using the Fe (II) -substituted MEL-type zeolite include nitrogen monoxide gas and hydrocarbon gas, which are gases contained in the exhaust gas of an internal combustion engine. Regarding hydrocarbon gas, alkanes such as methane, ethane, propane, butane, pentane, hexane, n-heptane and isooctane, alkenes such as ethylene, propylene, butene, pentene, methylpentene, hexene and methylhexene, benzene The Fe (II) -substituted MEL zeolite of the present invention is effective for adsorption of aromatics such as toluene, xylene and trimethylbenzene. When both nitric oxide and hydrocarbon are contained in the gas to be treated, both gases can be adsorbed at the same time by using the Fe (II) -substituted MEL zeolite of the present invention.

  The amount of Fe (II) contained in the Fe (II) -substituted MEL zeolite, that is, the supported amount is preferably 0.001 to 0.4 mmol / g with respect to the Fe (II) -substituted MEL zeolite. 0.001 to 0.3 mmol / g is more preferable, 0.001 to 0.2 mmol / g is still more preferable, and 0.001 to 0.15 mmol / g is still more preferable. By setting the amount of Fe (II) supported within this range, it is possible to effectively increase the adsorption efficiency of nitrogen monoxide and hydrocarbons.

The amount of Fe (II) supported in the Fe (II) -substituted MEL zeolite is measured by the following method. First, the Fe (II) -substituted MEL zeolite to be measured is weighed. This Fe (II) -substituted MEL zeolite is dissolved with hydrogen fluoride (HF), and the total amount of iron in the solution is quantified using an inductively coupled plasma emission spectrometer. Separately from this, the amount of Fe (III) in the Fe (II) -substituted MEL zeolite to be measured is measured by H 2 -TPR (temperature-reduction method). Then, the amount of Fe (II) is calculated by subtracting the amount of Fe (III) from the total amount of iron.

  In order to support Fe (II) ions on MEL-type zeolite, for example, the following method can be employed. MEL-type zeolite is dispersed in an aqueous solution of a divalent iron water-soluble compound and mixed by stirring. MEL type zeolite is preferably mixed at a ratio of 0.5 to 7 parts by mass with respect to 100 parts by mass of the aqueous solution. What is necessary is just to set the addition amount of the water-soluble compound of bivalent iron appropriately according to the grade of ion exchange.

  Mixing and stirring may be performed at room temperature or under heating. When mixing and stirring under heating, the liquid temperature is preferably set to 10 to 30 ° C. Further, the mixing and stirring may be performed in an air atmosphere or in an inert gas atmosphere such as a nitrogen atmosphere.

  In mixing and stirring, a compound for preventing divalent iron from being oxidized to trivalent iron may be added to water. As such a compound, ascorbic acid, which is a compound that does not hinder the ion exchange of Fe (II) ions and can prevent the Fe (II) ions from being oxidized to Fe (III) ions, is preferable. From the viewpoint of effectively preventing the oxidation of divalent iron, the amount of ascorbic acid added is 0.1 to 3 times, particularly 0.2 to 2 times the number of moles of divalent iron to be added. preferable.

  After mixing and stirring for a predetermined time, the solid content is suction filtered, washed with water and dried to obtain the target Fe (II) -substituted MEL zeolite. The X-ray diffraction pattern of this Fe (II) -substituted MEL zeolite is almost the same as the X-ray diffraction pattern of the MEL zeolite before supporting Fe (II) ions. That is, the crystal structure of zeolite is not changed by ion exchange.

The Fe (II) -substituted MEL-type zeolite used in the present invention has a SiO 2 / Al 2 O 3 ratio of 10 or more and 30 or less, preferably 12 or more and 24 or less, more preferably 12 or more and 21 or less. . That is, this Fe (II) -substituted MEL-type zeolite has a low SiO 2 / Al 2 O 3 ratio. Generally, a low SiO 2 / Al 2 O 3 ratio in zeolite means that the number of ion exchange sites is large. In other words, it means that the ability to carry Fe (II) ions is high. As a result of the study by the present inventors, surprisingly, in the Fe (II) -substituted MEL zeolite having a low SiO 2 / Al 2 O 3 ratio, nitrogen monoxide or hydrocarbon that can adsorb one Fe (II) ion can be used. It was found that the number of molecules could be increased. Therefore, by using the Fe (II) -substituted MEL zeolite of the present invention, it is possible to efficiently adsorb nitric oxide and hydrocarbon.

Fe (II) substituted MEL-type zeolite used in the present invention, in addition to having a SiO 2 / Al 2 O 3 ratio described above, BET specific surface area of 200~550m 2 / g, especially 200~450m 2 / g In particular, it is preferably 250 to 400 m 2 / g. The micropore specific surface area is preferably 180 to 450 m 2 / g, particularly 190 to 350 m 2 / g, and particularly preferably 190 to 280 m 2 / g. Further, the micropore volume is preferably 0.08 to 0.25 cm 3 / g, particularly preferably 0.10 to 0.20 cm 3 / g, and particularly preferably 0.10 to 0.15 cm 3 / g. By using the Fe (II) -substituted MEL zeolite having such physical property values, the adsorption characteristics of nitrogen monoxide and hydrocarbons are improved. As will be described later, these physical property values are not significantly different from the corresponding physical property values in the MEL-type zeolite before being ion-exchanged with Fe (II) ions.

  The Fe (II) -substituted MEL zeolite used in the present invention is particularly excellent in trapping properties of nitrogen monoxide and hydrocarbons discharged at the time of cold start of an internal combustion engine. The temperature of the three-way catalyst is not high enough at the cold start of the gasoline engine or diesel engine. By using the adsorbent (catalyst) containing the Fe (II) -substituted MEL zeolite used in the present invention, it is possible to trap nitrogen monoxide contained in a relatively low temperature exhaust gas at the time of cold start. Can be purified. When a few minutes have passed since the cold start and the operating temperature of the three-way catalyst is reached, the nitric oxide and hydrocarbon trapped in the Fe (II) -substituted MEL zeolite used in the present invention are released and released. Nitric oxide and hydrocarbons are purified by the three-way catalyst that has reached the operating temperature.

In the present invention, it is preferable to use MEL-type zeolite having specific physical property values as MEL-type zeolite that is ion-exchanged with Fe (II) ions. Specifically, the MEL type zeolite used in the present invention (hereinafter, this zeolite is referred to as “MEL type zeolite before substitution” in comparison with the Fe (II) substituted MEL type zeolite) is SiO 2 / Al 2. One of the features is that it is rich in aluminum with a low O 3 ratio. Specifically, the MEL-type zeolite before substitution is an aluminum-rich one whose SiO 2 / Al 2 O 3 ratio is preferably 10 or more and 30 or less, more preferably 12 or more and 24 or less. Such an aluminum-rich MEL-type zeolite before substitution preferably has a BET specific surface area measured in a sodium-type state of 190 to 420 m 2 / g, more preferably 190 to 370 m 2 / g. Moreover, the micropore specific surface area measured in a sodium-type state is preferably 200 to 550 m 2 / g, more preferably 380 to 500 m 2 / g. Further, the micropore volume measured in the sodium-type state is preferably 0.08 to 0.25 cm 3 / g, more preferably 0.10 to 0.20 cm 3 / g.

As described above, the values of SiO 2 / Al 2 O 3 ratio, BET specific surface area, micropore specific surface area and micropore volume in the MEL-type zeolite before substitution are the same as the corresponding values in the Fe (II) -substituted MEL-type zeolite. It does n’t change much.

The MEL-type zeolite before substitution includes sodium-type zeolite, and further includes those in which sodium ions are ion-exchanged with protons to form H + -type. When the MEL type zeolite is of the H + type, the above-mentioned measurement of the specific surface area and the like is performed after replacing protons with sodium ions. In order to convert the sodium type MEL type zeolite into the H + type, for example, the sodium type MEL type zeolite is dispersed in an aqueous ammonium salt solution such as ammonium nitrate, and the sodium ions in the zeolite are replaced with ammonium ions. By calcining this ammonium-type MEL-type zeolite, an H + -type MEL-type zeolite can be obtained.

  The above-mentioned specific surface area and volume are measured using a BET surface area measuring device as explained in the examples described later.

  The aluminum-rich pre-substitution MEL zeolite having the above physical properties is preferably produced by the production method described later. In the present invention, the reason why the MEL-type zeolite before substitution has achieved the physical properties described above is that the production method can suppress the occurrence of defects that may occur in the crystal structure of the obtained MEL-type zeolite before substitution. The details are not clear, although it is presumed that it was because of this.

Next, the suitable manufacturing method of the MEL type zeolite before substitution is demonstrated. The MEL-type zeolite before substitution is suitably produced by the method described in WO2012 / 002367A1 according to the applicant's previous application. In detail, it manufactures by the method of making the reaction mixture (gel) containing a silica source, an alumina source, an alkali source, and water react with the seed crystal of MEL type zeolite. When the zeolite is synthesized only from the gel as the gel, the synthesized zeolite is at least one of the composite building units of the MEL zeolite that is the target zeolite as the composite building unit. A gel having a composition including one kind is used. MEL-type zeolite has a skeletal structure formed from three composite building units of mor, mel and mfi, and mordenite, a zeolite containing at least one of these three composite building units, is produced. If a gel having such a composition is used, it is possible to easily obtain a MEL-type zeolite having a low SiO 2 / Al 2 O 3 ratio, which is the target zeolite.

Specifically, the gel, that is, the gel having a composition that forms mordenite, preferably has a silica source and an alumina source so as to have a composition represented by the molar ratio shown in the following (a) or (b). A mixture of an alkali source and water may be used.
(A)
SiO 2 / Al 2 O 3 = 40 to 200, especially 44 to 200
Na 2 O / SiO 2 = 0.24~0.4 , in particular 0.25 to 0.35
H 2 O / SiO 2 = 10-50, especially 15-25
(B)
SiO 2 / Al 2 O 3 = 10-40, especially 12-40
Na 2 O / SiO 2 = 0.05 to 0.25, especially 0.1 to 0.25
H 2 O / SiO 2 = 5-50, especially 10-25

On the other hand, the seed crystal can be synthesized by a conventional method using an organic structure directing agent (hereinafter referred to as “organic SDA”). For example, tetrabutylammonium hydroxide can be used as the organic structure directing agent preferably used for the synthesis of MEL-type zeolite. The organic structure directing agent is stirred and heated in water together with an alumina source and a silica source to obtain MEL-type zeolite as a seed crystal. Since the obtained zeolite is in a state containing an organic structure-directing agent, the organic structure-directing agent is removed by calcination in air. The MEL-type zeolite as a seed crystal thus obtained has a SiO 2 / Al 2 O 3 ratio of about 30 to 70.

A preferred method for producing the pre-substitution MEL zeolite will be described in more detail with reference to FIG. In the present invention, in the figure, the production can be performed in the order of <1>, <2>, <3>, <6>. Employing this procedure, a wide range of SiO 2 / Al 2 O 3 ratio zeolites can be produced. In the figure, the production can also be performed in the order of <1>, <2>, <4>, <3>, <6>. If this procedure is adopted, a seed crystal having a low SiO 2 / Al 2 O 3 ratio can often be effectively used by standing and heating after aging. Furthermore, in FIG. 1, it can also manufacture in order of <1>, <2>, <4>, <5>, <6>. In this procedure, aging and stirring operations are performed.

  In each of the above procedures, a reaction mixture (gel) containing a seed crystal is placed in a sealed container and heated to react to crystallize the target MEL-type zeolite. This gel does not contain organic SDA. The aging in the above procedure refers to an operation of maintaining the temperature at a temperature lower than the reaction temperature for a certain time. In aging, generally, it is left without stirring. It is known that effects such as prevention of by-product impurities, enabling heating under stirring without by-product impurities, and increasing the reaction rate can be achieved by aging. . However, the mechanism of action is not always clear. The temperature and time for aging are set so that the above-mentioned effects are maximized. In the present invention, aging is preferably performed at 20 to 80 ° C., more preferably 20 to 60 ° C., and preferably in the range of 2 hours to 1 day.

  In the case of stirring for the purpose of making the temperature of the gel uniform during heating, by-growth of impurities can be prevented by heating and stirring after aging (<1>, <2>, <4> , <5>, <6> procedure). Stirring is performed to make the composition and temperature of the gel uniform, and includes mixing by a stirring blade and mixing by rotating a container. What is necessary is just to adjust stirring intensity | strength and rotation speed according to the uniformity of temperature, and the byproduct of an impurity. Instead of constant stirring, intermittent stirring may be used. Thus, industrial mass production becomes possible by combining aging and stirring.

  In both the stationary method and the stirring method, the heating temperature is in the range of 100 to 200 ° C, preferably 120 to 180 ° C, and heating is performed under an autogenous pressure. If the temperature is lower than 100 ° C., the crystallization rate becomes extremely slow, and the production efficiency of MEL-type zeolite may deteriorate. On the other hand, when the temperature exceeds 200 ° C., an autoclave having a high pressure resistance is required, which is not economical, and the generation rate of impurities increases. The heating time is not critical in the present production method, and it may be heated until a MEL type zeolite having sufficiently high crystallinity is produced. In general, satisfactory crystalline MEL zeolite can be obtained by heating for about 5 to 240 hours.

  By the heating described above, the desired crystals of MEL-type zeolite before substitution are obtained. After completion of the heating, the produced crystal powder is separated from the mother liquor by filtration, washed with water or warm water and dried. The obtained crystals of MEL-type zeolite before substitution do not need to be calcined because they do not contain organic substances in a dry state, and can be used immediately after dehydration.

  Examples of the silica source used for the reaction include silica itself and silicon-containing compounds capable of generating silicate ions in water. Specific examples include wet method silica, dry method silica, colloidal silica, sodium silicate, aluminosilicate gel, and the like. These silica sources can be used alone or in combination of two or more. Among these silica sources, it is preferable to use silica (silicon dioxide) in that a zeolite can be obtained without unnecessary by-products.

  As the alumina source, for example, a water-soluble aluminum-containing compound can be used. Specific examples include sodium aluminate, aluminum nitrate, and aluminum sulfate. Aluminum hydroxide is also a suitable alumina source. These alumina sources can be used alone or in combination of two or more. Of these alumina sources, it is preferable to use sodium aluminate or aluminum hydroxide because zeolite can be obtained without unnecessary by-products (for example, sulfate, nitrate, etc.).

As the alkali source, for example, sodium hydroxide can be used in the case of sodium. When sodium silicate is used as the silica source or sodium aluminate is used as the alumina source, sodium which is an alkali metal component contained therein is simultaneously regarded as NaOH and is also an alkali component. Therefore, the Na 2 O is calculated as the sum of all alkali components in the reaction mixture (gel).

  The order of addition of each raw material when preparing the reaction mixture may be a method in which a uniform reaction mixture is easily obtained. For example, a uniform reaction mixture can be obtained by adding and dissolving an alumina source and a lithium source in an aqueous sodium hydroxide solution at room temperature, and then adding a silica source and stirring. The seed crystals are added with mixing with the silica source or after the silica source is added. Thereafter, stirring and mixing are performed so that the seed crystals are uniformly dispersed. There is no restriction | limiting in particular also in the temperature at the time of preparing a reaction mixture, Generally, it may carry out at room temperature (20-25 degreeC).

  The MEL-type zeolite before substitution thus obtained is ion-exchanged with Fe (II) ions as described above to become a Fe (II) -substituted MEL type zeolite. The Fe (II) -substituted MEL zeolite may be used as it is as an adsorbent for various gases such as nitric oxide and hydrocarbon, or as a gas adsorbent containing the Fe (II) -substituted MEL zeolite. May be. Regardless of the form of the Fe (II) -substituted MEL-type zeolite, the Fe (II) -substituted MEL-type zeolite is brought into solid-gas contact with various gases such as nitric oxide and hydrocarbon, whereby the gas is converted into Fe (II). II) Can be adsorbed on substituted MEL-type zeolite.

  In the present invention, in addition to adsorbing the nitric oxide gas or hydrocarbon gas by bringing the nitric oxide gas or hydrocarbon gas itself into contact with the Fe (II) -substituted MEL zeolite, the nitric oxide gas or hydrocarbon gas is adsorbed. A gas containing gas may be brought into contact with the Fe (II) -substituted MEL zeolite to adsorb nitrogen monoxide gas or hydrocarbon gas in the gas and remove nitrogen monoxide gas or hydrocarbon gas from the gas. it can. Examples of such gas include exhaust gas of an internal combustion engine using hydrocarbons such as gasoline and light oil as fuel, exhaust gas generated from various boilers and incinerators, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” means “mass%”. The analytical instruments used in the following examples, comparative examples and reference examples are as follows.
Powder X-ray diffractometer: manufactured by Mac Science Co., Ltd., powder X-ray diffractometer MO3XHF 22 , using Cukα ray, voltage 40 kV, current 30 mA, scan step 0.02 °, scan speed 2 ° / min
SiO 2 / Al 2 O 3 ratio: MEL-type zeolite was dissolved using hydrogen fluoride (HF), and the solution was analyzed using ICP to quantify Al. Further, MEL-type zeolite was dissolved using potassium hydroxide (KOH), and the solution was analyzed using ICP to quantify Si. The SiO 2 / Al 2 O 3 ratio was calculated based on the determined amounts of Si and Al.
BET surface area, micropore specific surface area and micropore volume measuring device: AUTOSORB-1 manufactured by Cantachrome Instruments Co., Ltd.

[Example 1]
(1) Production of MEL-type zeolite before substitution This is an example of producing an Fe (II) -substituted MEL-type zeolite having a SiO 2 / Al 2 O 3 ratio of 19.0. An aqueous solution was obtained by dissolving 0.113 g of sodium aluminate and 2.582 g of 36% sodium hydroxide in 12.88 g of pure water. A mixture of 2.427 g of finely divided silica (Cab-O-Sil, M-5) and 0.243 g of seed crystals was added little by little to the aqueous solution and mixed by stirring to obtain a gel. The seed crystal was manufactured by the following method. This gel has an SiO 2 / Al 2 O 3 ratio of 100, an Na 2 O / SiO 2 ratio of 0.300, and an H 2 O / SiO 2 ratio of 20. When zeolite is synthesized from only this, mordenite (MOR ). The mixture of the gel and the seed crystal was put in a 60 cc stainless steel sealed container and allowed to stand at 140 ° C. for 15 hours under an autogenous pressure without aging and stirring. After cooling the sealed container, the product was filtered and washed with warm water to obtain a white powder. This product was a MEL-type zeolite containing no impurities. Table 1 shows the physical property values of the pre-substitution MEL type zeolite thus obtained.

[Method for producing MEL-type zeolite seed crystal]
MEL type zeolite is obtained by stirring and heating by a conventionally known method using tetraethylammonium hydroxide as organic SDA, sodium aluminate as an alumina source, and fine powder silica (Cab-O-Sil, M-5) as a silica source. Obtained. The conditions for stirring and heating are 180 ° C. and 96 hours. The SiO 2 / Al 2 O 3 ratio of the MEL type zeolite was 34.0. This was baked at 550 ° C. for 10 hours while circulating air in an electric furnace to produce a crystal containing no organic matter. From the result of X-ray diffraction, it was confirmed that this crystal was MEL type zeolite. This MEL type zeolite did not contain SDA. This MEL type zeolite was used as a seed crystal.

(2) Production of Fe (II) -substituted MEL-type zeolite After adding 60 ml of distilled water, 1 g of MEL-type zeolite before substitution and ascorbic acid twice as many as the iron compound to be added to a polypropylene container, Fe (II) SO the 4 · 7H 2 O, was added 10 wt% with respect to the front-substituted MEL-type zeolite, under a nitrogen atmosphere and stirred at room temperature for 1 day. Thereafter, the precipitate was filtered by suction, washed with distilled water, and dried to obtain Fe (II) -substituted MEL zeolite carrying Fe 2+ at 0.041 mmol / g. The amount of Fe 2+ supported was determined by the method described above. When XRD measurement was performed on the obtained Fe (II) -substituted MEL-type zeolite, it was observed that the peak position and peak intensity were almost the same as those of the MEL-type zeolite before substitution, and the structure of the MEL-type zeolite was maintained after ion exchange. It was confirmed that

(3) Evaluation of Nitric Oxide Gas Adsorption After accurately weighing 20 mg of Fe (II) -substituted MEL type zeolite with an electronic balance, 180 mg of silicon carbide was used as a diluent and both were mixed evenly. The mixture was packed in a quartz glass tube having an inner diameter of 6 mm. The adsorbed water during mixing was removed by heating with a mantle heater, and then cooled to room temperature. Next, 10 cm3 of nitric oxide gas was pulsed at room temperature for 5 cm 3 every 2 minutes in the quartz glass tube. The amount of nitric oxide gas that was not adsorbed and came out of the quartz glass tube was measured using the peak area of a thermal conductivity gas chromatograph (GC-TCD, manufactured by Shimadzu Corporation, GC-8A) and a chemiluminescent NO analyzer (NOx). It was calculated from the value detected by analyzer, manufactured by Yanagimoto Seisakusho, ECL-77A). The measurement conditions of the thermal conductivity gas chromatograph (GC-TCD) are as shown below. Then, the amount of nitric oxide gas adsorbed on the Fe (II) -substituted MEL zeolite per unit mass was determined by subtracting the calculated value from the supply amount of nitric oxide gas. The results are shown in Table 1 below.

[Measurement conditions of thermal conductivity gas chromatograph (GC-TCD)]
・ Carrier gas: He gas ・ Carrier gas flow rate: 30 cm 3 · min −1
・ Detector temperature: 100 ° C
・ Detector current: 80 mA

(4) Toluene gas adsorption evaluation Toluene, which is a typical hydrocarbon contained in exhaust gas discharged from an internal combustion engine, was used as an adsorption target gas. 20 mg of Fe (II) -substituted MEL-type zeolite was put in a quartz tube having an inner diameter of 4 mm and held between quartz wool and glass beads. Helium was used as the mobile phase and the sample was activated at 390 ° C. for about 1 hour. After cooling the column to 50 ° C., toluene was injected until saturated. The amount of toluene gas that was not adsorbed and emerged from the quartz glass tube was calculated from the value detected by the peak area of the thermal conductivity gas chromatograph (GC-TCD, manufactured by Shimadzu Corporation, GC-8A). The measurement conditions of the thermal conductivity gas chromatograph (GC-TCD) are as shown below. Then, the amount of toluene gas adsorbed on the Fe (II) -substituted MEL zeolite per unit mass was determined by subtracting the calculated value from the supply amount of toluene gas. The results are shown in Table 1 below.

[Measurement conditions of thermal conductivity gas chromatograph (GC-TCD)]
・ Carrier gas: He gas ・ Carrier gas flow rate: 30 cm 3 · min −1
・ Detector temperature: 150 ° C
・ Detector current: 50 mA

[Examples 2 and 3]
Fe (II) SO 4 .7H 2 O was added in the same manner as in Example 1 except that 20% by mass (Example 2) and 40% by mass (Example 3) were added to the MEL-type zeolite before substitution. ) A substituted MEL-type zeolite was obtained. The amount of Fe 2+ supported was as shown in Table 1. Evaluation similar to Example 1 was performed about the obtained Fe (II) substituted MEL type | mold zeolite. The results are shown in Table 1.

Example 4
(1) Production of MEL-type zeolite before substitution This is an example of producing an Fe (II) -substituted MEL-type zeolite having a SiO 2 / Al 2 O 3 ratio of 15.4. In Example 1, a gel composition having a SiO 2 / Al 2 O 3 ratio of 30, a Na 2 O / SiO 2 ratio of 1.93, and an H 2 O / SiO 2 ratio of 20 was used. Further, MEL type zeolite having a SiO 2 / Al 2 O 3 ratio of 66.0 was used as a seed crystal. This seed crystal was produced using tetraethylammonium hydroxide as organic SDA, as in Example 1. A white powder was obtained in the same manner as in Example 1 except for this. When this product was subjected to XRD measurement, it was confirmed that this product was a MEL-type zeolite containing no impurities such as SDA. Table 1 shows the physical property values of the pre-substitution MEL type zeolite thus obtained.

(2) Production of Fe (II) -substituted MEL-type zeolite After adding 60 ml of distilled water, 1 g of MEL-type zeolite before substitution and ascorbic acid twice as many as the iron compound to be added to a polypropylene container, Fe (II) SO the 4 · 7H 2 O, was added 10 wt% with respect to the front-substituted MEL-type zeolite, under a nitrogen atmosphere and stirred at room temperature for 1 day. Thereafter, the precipitate was filtered by suction, washed with distilled water, and dried to obtain Fe (II) -substituted MEL zeolite carrying Fe 2+ at 0.029 mmol / g. When XRD measurement was performed on the obtained Fe (II) -substituted MEL zeolite and the MEL-type zeolite before substitution, it was observed that the peak position and peak intensity remained almost unchanged, and the structure of the MEL-type zeolite was maintained after ion exchange. It was confirmed that Evaluation similar to Example 1 was performed about the obtained Fe (II) substituted MEL type | mold zeolite. The results are shown in Table 1.

[Examples 5 and 6]
Fe (II) SO 4 .7H 2 O was added in the same manner as in Example 4 except that 20% by mass (Example 5) and 40% by mass (Example 6) were added to the MEL-type zeolite before substitution. ) A substituted MEL-type zeolite was obtained. The amount of Fe 2+ supported was as shown in Table 1. Evaluation similar to Example 1 was performed about the obtained Fe (II) substituted MEL type | mold zeolite. The results are shown in Table 1.

  As is clear from the results shown in Table 1, it can be seen that the use of the Fe (II) -substituted MEL zeolite obtained in each Example can efficiently adsorb and remove nitrogen monoxide gas and toluene gas.

Claims (11)

  1. A Fe (II) -substituted MEL-type zeolite having a SiO 2 / Al 2 O 3 ratio of 10 or more and 30 or less and ion-exchanged with Fe (II) ions.
  2.   The Fe (II) -substituted MEL zeolite according to claim 1, wherein the supported amount of Fe (II) is 0.001 to 0.4 mmol / g with respect to the Fe (II) -substituted MEL zeolite.
  3. The Fe (II) -substituted MEL according to claim 1 or 2, wherein the MEL-type zeolite before being ion-exchanged with Fe (II) ions has a SiO 2 / Al 2 O 3 ratio of 10 or more and 30 or less. Type zeolite.
  4. The BET specific surface area is 200 to 550 m 2 / g, the micropore specific surface area is 180 to 450 m 2 / g, and the micropore volume is 0.10 to 0.20 cm 3 / g. The Fe (II) -substituted MEL zeolite according to any one of the above.
  5.   A gas adsorbent comprising the Fe (II) -substituted MEL zeolite according to any one of claims 1 to 4.
  6.   The gas adsorbent according to claim 5, which is used for adsorption of nitric oxide.
  7.   The gas adsorbent according to claim 5, which is used for adsorption of hydrocarbon.
  8. An MEL type zeolite having a SiO 2 / Al 2 O 3 ratio of 10 or more and 30 or less is dispersed in a divalent iron water-soluble compound aqueous solution and mixed and stirred, whereby Fe (II) ions are added to the MEL type zeolite. A process for producing Fe (II) -substituted MEL-type zeolite, which comprises a step of supporting.
  9.   The manufacturing method according to claim 8, wherein ascorbic acid is added to the aqueous solution in an amount of 0.1 to 3 times the number of moles of the divalent iron during the mixing and stirring.
  10. Contacting the Fe (II) -substituted MEL zeolite having a SiO 2 / Al 2 O 3 ratio of 10 or more and 30 or less and ion-exchanged with Fe (II) ions with nitrogen monoxide or a gas containing nitric oxide; A method for removing nitric oxide by adsorbing nitric oxide on the Fe (II) -substituted MEL-type zeolite.
  11. The SiO 2 / Al 2 O 3 ratio is 10 or more and 30 or less, and the Fe (II) -substituted MEL type zeolite ion-exchanged with Fe (II) ions is brought into contact with hydrocarbon or a gas containing hydrocarbon to obtain hydrocarbon. For removing hydrocarbons by adsorbing to the Fe (II) -substituted MEL-type zeolite.
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CN201810470599.3A CN108640127A (en) 2012-07-18 2013-07-16 Fe (II) replaces the removing method of MEL types zeolite and its preparation method, the adsorbent comprising it and nitric oxide and hydrocarbon
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